CN106076377A - A kind of cobalt sulfide nickel carbon nanotube carbon nano-fiber composite material of phosphorus doping and preparation method thereof - Google Patents
A kind of cobalt sulfide nickel carbon nanotube carbon nano-fiber composite material of phosphorus doping and preparation method thereof Download PDFInfo
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- CN106076377A CN106076377A CN201610387840.7A CN201610387840A CN106076377A CN 106076377 A CN106076377 A CN 106076377A CN 201610387840 A CN201610387840 A CN 201610387840A CN 106076377 A CN106076377 A CN 106076377A
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
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Abstract
The invention belongs to transient metal sulfide material with carbon element technical field, cobalt sulfide nickel carbon nanotube carbon nano-fiber composite material of a kind of phosphorus doping and its preparation method and application.Preparation process of the present invention includes: prepared the carbon nano-fiber mixing CNT by electrostatic spinning and high temperature cabonization method, again by hydro-thermal method growth in situ cobalt sulfide nanosized nickel rods, last under inert gas atmosphere, the phosphorous presoma of high-temperature calcination, it is achieved the composite of phosphorus doping.Carbon nano-fiber prepared by the present invention has bigger specific surface area, wherein mixes CNT, can effectively strengthen electric conductivity；As substrate, cobalt sulfide nanosized nickel rods is grown in composite fiber surface uniformly, densely, can give full play to the synergism of various material；Introduce phosphorus doping and can improve the electro-chemical activity of composite further.The cobalt sulfide nickel carbon nanotube carbon nano-fiber composite material of phosphorus doping prepared by the present invention can be as high-performance electric catalysis material, and the electrode material of the new energy devices such as lithium ion battery and solaode.
Description
Technical field
The invention belongs to transient metal sulfide-material with carbon element technical field, be specifically related to the cobalt sulfide nickel of a kind of phosphorus doping/
CNT-carbon nano-fiber composite material and preparation method thereof.
Background technology
Carbon nano-fiber, due to its higher surface area and structural stability, is widely used in electrochemical field.And it is quiet
The method that Electrospinning provides a low cost, carbon nano-fiber is prepared in scale, and the microstructure of its fiber can
With flexible modulation.Can uniformly mix many kinds of substance in spinning liquid and carry out blending, to strengthen the many property of carbon nano-fiber
Energy.As base material, growth in situ has the material of electro-chemical activity, can fully realize good the working in coordination with of many kinds of substance
Effect, to prepare the composite of excellent performance.
In recent years, being inspired by azotase and hydrogenase structure and composition, Transition-metal dichalcogenide is used for electricity
Chemical catalysis material.Research finds, cobalt sulfide, cobaltous selenide etc. present the catalytic activity for hydrogen evolution of excellence, and its performance is even better than
Traditional two-dimensional slice structural transition metal chalcogenide compound, such as molybdenum bisuphide and tungsten disulfide.And bimetallic transition metal
For chalcogenide is compared to monometallic chalcogenide, there is higher electric conductivity, but its relevant research report
Lead actually rare.Cobalt sulfide nickel is exactly the bimetallic sulfide of a quasi-representative, has the advantages such as easily prepared, morphology controllable.But
It is that pure cobalt sulfide nickel is prone to autohemagglutination so that it is avtive spot cannot fully be exposed, and has had a strong impact on its catalysis characteristics and energy
The cyclical stability of amount storage.Therefore, carry out the carbon nanomaterial of cobalt sulfide nickel Yu excellent in stability being effectively combined and there is weight
Want meaning.
Except electroactive substance is nano-structured, structure doping is that one is effectively improved integral material electrification equally
The method learning activity.At catalytic field, it can regulate the internal electron transmission structure of catalyst, optimizes Hydrogen chemisorption energy
Amount, improves catalytic reaction activity from mechanism.In the energy storage such as ultracapacitor and lithium ion battery field, Heteroatom doping can
To improve its stored energy capacitance.Conventional Heteroatom doping has nitrogen, phosphorus, and selenium adulterates, and the mode of Effective Doping can use lazy
To carrying out high-temperature calcination decomposition containing hetero atom precursor species under property air-flow, the material being positioned at airflow downstream just can successfully be mixed
Miscellaneous.
The present invention by simple technological design, prepare the cobalt sulfide nickel carbon nanotube of a kind of novel phosphorus doping-
Carbon nano-fiber composite material.This composite has the advantage that Static Spinning carbon nano-fiber has the three-dimensional porous of uniqueness
Structure, higher specific surface area and excellent mechanical property, and the incorporation of CNT can improve the conduction of material further
Property；Cobalt sulfide nanosized nickel rods is grown on carbon nano-fiber equably, can effectively suppress the reunion of himself so that it is avtive spot
More fully exposed；The mechanical property of carbon nano-fiber excellence makes composite be applied to urge as flexible electrode material
Change and in energy storage device；Cobalt sulfide nickel itself possesses higher catalysis activity and theoretical stored energy capacitance value, introduces substrate
Matter is allowed to present nano-structured growth morphology, and excellent electro-chemical activity is given full play to；And phosphorus doping more can be adjusted
Economize on electricity lotus distributed architecture, further enhances catalysis activity and energy storage capacity.Therefore, by phosphorus doping, cobalt sulfide nickel, carbon nanometer
Pipe and carbon nano-fiber are effectively combined, it is possible to achieve synergism good between many persons, to prepare excellent performance
Composite.
Summary of the invention
It is an object of the invention to provide the cobalt sulfide nickel carbon nanotube-carbon of the phosphorus doping of a kind of electrochemical performance
Nano-fiber composite material and preparation method thereof.
The cobalt sulfide nickel carbon nanotube-carbon nano-fiber composite material of the phosphorus doping that the present invention provides, it prepares raw material group
One-tenth includes: polyacrylonitrile, CNT,N,N-Dimethylformamide, cobalt salt, nickel salt, sulfosalt, auxiliary agent etc..
The cobalt sulfide nickel carbon nanotube-carbon nano-fiber composite material of the phosphorus doping that the present invention provides, its preparation process bag
Include: prepare CNT-polyacrylonitrile nanofiber film by electrostatic blended spinning, then through pre-oxidation, prepared by high temperature cabonization
Obtain CNT-carbon nano-fiber composite membrane, then one step hydro thermal method growth in situ cobalt sulfide nanosized nickel rods on composite membrane,
The composite of phosphorus doping is realized finally by the calcining of phosphorous presoma.Specifically comprise the following steps that
(1) polyacrylonitrile powder and acidifying CNT are joinedN,N-In solvent dimethylformamide, continuously stirred, obtain
Homogeneous, the CNT-polyacrylonitrile mixed dispersion liquid of thickness；
(2) mixed dispersion liquid obtained is carried out electrostatic spinning, obtain CNT-polyacrylonitrile nanofiber blending film；
(3) blending film is pre-oxidized in air atmosphere, the CNT after being pre-oxidized-polyacrylonitrile nanofiber film；
(4) fibrous membrane after pre-oxidation is carried out high temperature cabonization under inert gas shielding, obtain CNT-carbon nano-fiber
Film；
(5) by soluble in water to cobalt salt, nickel salt, sulfosalt and auxiliary agent, homogeneous saline solution is prepared；
(6) saline solution step (5) obtained and carbon nanofiber membrane carry out hydro-thermal reaction, obtain cobalt sulfide nickel carbon nanotube-
Carbon nano-fiber composite material；
(7) composite that step (6) obtains being carried out phosphating reaction, phosphorous presoma is placed in inert atmosphere upstream, composite wood
Material is placed in downstream, calcines a period of time in tube furnace, and the cobalt sulfide nickel carbon nanotube-carbon nano-fiber obtaining phosphorus doping is multiple
Condensation material.
In the present invention, the electrostatic spinning described in step (2), its process conditions are: electrostatic field voltage 15 ~ 25 kV, spinning
Speed 0.2 ~ 0.4 mm min-1, receiving range 17 ~ 26 cm, the mass fraction of polyacrylonitrile is 7 % ~ 12 %, CNT with
The mass ratio of polyacrylonitrile is 0.01 ~ 0.1.
In the present invention, in the preoxidation process described in step (3), heating rate is 1 ~ 2 DEG C of min-1, the temperature of pre-oxidation
Degree is 220 ~ 280 DEG C, and preoxidation time is 1 ~ 2 h.
In the present invention, during the high temperature cabonization described in step (4), described noble gas is high-purity argon gas or High Purity Nitrogen
Gas, high temperature cabonization temperature is 800 ~ 1500 DEG C, and the high temperature cabonization time is 1 ~ 3 h.
In the present invention, in step (5), described cobalt salt is selected from cobalt chloride, cobalt nitrate, cobaltous acetate；Nickel salt is selected from nitric acid
Nickel, Nickel dichloride., nickel sulfate；Sulfosalt is selected from thiourea, thioacetamide, sodium sulfide；Auxiliary agent is selected from carbamide, hexamethylenetetramine, second
Diamidogen；Mass range 10 ~ 30 mg mL of cobalt salt-1;Mass range 5 ~ 15 mg mL of nickel salt-1;The mass range of sulfosalt is
15~30 mg mL-1, the mass range of auxiliary agent is 5 ~ 15 mg mL-1。
In the present invention, in step (6), the temperature of hydro-thermal reaction is 150 ~ 200 DEG C, and the response time is 10 ~ 24 h.
In the present invention, in step (7), phosphorous presoma is sodium hypophosphite, and consumption is 5 ~ 20 times of composite cellulosic membrane, high temperature
Calcining heat is 300 ~ 900 DEG C.
Scanning electron microscope (SEM), X-ray diffractometer (XRD), electrochemical workstation is used to characterize the present invention and obtained
The structure and morphology of the cobalt sulfide nickel carbon nano-fiber composite material of the phosphorus doping obtained, its result is as follows:
(1) SEM test result shows: after mixing CNT, carbon nano-fiber surface becomes coarse, and there is exposure some areas
The vestige of CNT, electrical conductivity is significantly increased, close to 3 times of pure carbon nano-fiber.Cobalt sulfide nickel carbon at phosphorus doping
In nano-fiber composite film, cobalt sulfide nanosized nickel rods is grown on carbon nano-fiber shows equably, takes full advantage of carbon nanometer
The high-specific surface area of fiber and high conductivity, effectively inhibit the reunion of cobalt sulfide nickel self so that it is electro-chemical activity site obtains
To fully exposing.Additionally, EDS collection of illustrative plates proves that P elements is introduced in composite, adulterate successfully.See accompanying drawing 1 and accompanying drawing 2；
(2) XRD test result shows, the prepared composite before and after phosphorus doping goes out peak position and do not changes, at 2 θ
=16.3 °, 27.3 °, 32.0 °, 38.7 °, 47.8 °, 50.9 °, 55.5 ° have obvious diffraction maximum, corresponding to the sulfur of Emission in Cubic
Change (111) of cobalt nickel, (220), (311), (400), (422), (511) and (440) crystal face (JCPDS20-0782), discuss further
Card is before and after phosphatization, and the material of cobalt sulfide nickel does not change itself.See accompanying drawing 3；
(3) electro-chemical test shows, the cobalt sulfide nickel carbon nanotube of prepared phosphorus doping-carbon nano-fiber composite material tool
Having the electrochemical catalysis Hydrogen Evolution Performance of excellence, its initial overpotential is-0.025 V, and Tafel slope is 60.3 mV/decade,
It is far superior to the performance of unadulterated cobalt sulfide nickel carbon nanotube-carbon nano-fiber composite material.See accompanying drawing 4.
It is an advantage of the current invention that:
(1) preparation process is simple, it is easy to operation, is a kind of convenient effective preparation method；
(2) experimental design is ingenious.It is successfully prepared cobalt sulfide nanosized nickel rods/CNT-carbon Nanowire by one step hydro thermal method
Dimension composite, unique Rod-like shape makes electro-chemical activity site fully be exposed.Calcine further through phosphorous presoma
Method, introduces phosphorus doping simply and effectively, improves its chemical property further；
(3) the cobalt sulfide nickel carbon nanotube-carbon nano-fiber composite material of the phosphorus doping prepared by can be used as liberation of hydrogen, hydrogen reduction
The ideal electrode material of catalyst material and the new energy devices such as ultracapacitor, lithium ion battery.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the carbon nano-fiber of the CNT incorporation of embodiment 1 in the present invention.
Fig. 2 is that the cobalt sulfide nickel carbon nanotube-carbon nano-fiber SEM figure of the phosphorus doping of embodiment 1 in the present invention is with corresponding
EDS collection of illustrative plates.
Fig. 3 is the cobalt sulfide nickel carbon nanotube-carbon nano-fiber composite wood in the present invention before and after the phosphorus doping of embodiment 1
The XRD figure of material.
Fig. 4 is the cobalt sulfide nickel carbon nanotube-carbon nano-fiber composite material before and after the phosphorus doping of the embodiment of the present invention 1
Electrochemical catalysis Hydrogen Evolution Performance figure, (A) linear sweep voltammetry curve (LSV), (B) Tafel curve.
Detailed description of the invention
Below in conjunction with instantiation, the present invention is expanded on further.Should be understood that these embodiments be merely to illustrate the present invention and
It is not used in restriction the scope of the present invention.Additionally, after having read the content that the present invention lectures, those skilled in the art can be right
The present invention makes various change or amendment, and these equivalent form of values fall within the application appended claims limited range equally.
Embodiment 1, the present embodiment comprise the following steps:
(1) 1 g polyacrylonitrile powder and 35 mg are acidified CNT and join 10 mLN,N-Solvent dimethylformamide
In, continuously stirred, prepare homogeneous thickness dispersion liquid；
(2) mixed dispersion liquid obtained being carried out electrostatic spinning, its regulation technological parameter is: electrostatic field voltage 20 kV, spinning speed
Spend 0.3 mm min-1, receiving range 20 cm, prepare CNT-polyacrylonitrile composite fiber film；
(3) being pre-oxidized in air atmosphere by the blending film obtained, the temperature of pre-oxidation is 250 DEG C, and heating rate is 1 DEG C
min-1, preoxidation time is 1h, prepares the CNT after pre-oxidation-polyacrylonitrile nanofiber film；
(4) gained blending film being carried out in high pure nitrogen high temperature cabonization, high temperature cabonization temperature is 800 DEG C, the high temperature cabonization time
It is 2 h, prepares CNT-carbon nano-fiber composite membrane；
(5) by 580 mg cobalt nitrates, 290 mg nickel nitrates, 609 mg thiourea and 240 mg carbamide are dissolved in 30 mL deionized waters,
Ultrasonic 5min, prepares homogeneous saline solution；
(6) blending film in (4) is immersed saline solution in (5), hydro-thermal reaction 12 h at 160 DEG C, obtain cobalt sulfide nickel carbon and receive
Mitron-carbon nanofiber membrane；
(7) composite that step (6) obtains is carried out phosphating reaction, is placed in inert atmosphere upstream containing 100 mg sodium hypophosphites,
Composite is put in downstream, and in tube furnace, 300 DEG C of calcining 2 h, obtain the cobalt sulfide nickel carbon nanotube-carbon nanometer of phosphorus doping
Fibrous composite, is designated as P dopedCNT-CNF@NiCo2S4。
Embodiment 2, step (7) in embodiment 1 being not added with phosphorus source, remaining is all with embodiment 1, the composite wood finally obtained
Material is designated as CNT-CNF@NiCo2S4, it is-0.125 V that its liberation of hydrogen initiates overpotential, and Tafel slope is 66.7 mV/decade, property
The composite after phosphorus doping can be worse than, see accompanying drawing 4.
Embodiment 3, the sodium hypophosphite consumption of step (7) in embodiment 1 being become 500 mg, remaining is all with embodiment 1,
The composite obtained eventually is designated as P dopedCNT-CNF@NiCo2S4-1, Hydrogen Evolution Performance is close with example 1.
Embodiment 4, the hydrothermal temperature of step (6) in embodiment 1 being become 180 DEG C, remaining is all with embodiment 1,
The composite obtained eventually is designated as P dopedCNT-CNF@NiCo2S4-2, Hydrogen Evolution Performance is close with example 1.
In electro-chemical test, use three electrode test systems, with the glass-carbon electrode that prepared hybrid material is modified be
Working electrode, saturated calomel electrode is reference electrode, and graphite rod is to electrode, and electrolyte is 0.5 M H2SO4.Before testing, in advance
First electrolyte is led to nitrogen 30 min.Use the electro-catalysis of hybrid material prepared in the linear sweep voltammetry research present invention
Evolving hydrogen reaction activity.
Claims (9)
1. the preparation method of the cobalt sulfide nickel carbon nanotube-carbon nano-fiber composite material of a phosphorus doping, it is characterised in that:
Prepare CNT-polyacrylonitrile nanofiber film by electrostatic cospinning, then through pre-oxidation and high temperature cabonization, obtain carbon
Nanotube-carbon nanofiber membrane, then by one step hydro thermal method growth in situ cobalt sulfide nanosized nickel rods on composite fibre, finally
Presoma calcining is utilized to realize phosphorus doping；Specifically comprise the following steps that
(1) polyacrylonitrile powder and acidifying CNT are joinedN,N-In solvent dimethylformamide, continuously stirred, obtain
Homogeneous, the CNT-polyacrylonitrile mixed dispersion liquid of thickness；
(2) mixed dispersion liquid obtained is carried out electrostatic spinning, obtain CNT-polyacrylonitrile nanofiber blending film；
(3) being pre-oxidized in air atmosphere by the blending film obtained, the CNT after being pre-oxidized-polyacrylonitrile nano is fine
Dimension film；
(4) fibrous membrane after pre-oxidation is carried out high temperature cabonization under inert gas shielding, obtain CNT-carbon nano-fiber
Film；
(5) by soluble in water to cobalt salt, nickel salt, sulfosalt and auxiliary agent, homogeneous saline solution is prepared；
(6) carbon nanofiber membrane that saline solution step (5) obtained and step (4) obtain carries out hydro-thermal reaction, is vulcanized
Cobalt nickel carbon nanotube-carbon nano-fiber composite material；
(7) composite that step (6) obtains being carried out phosphating reaction, phosphorous presoma is placed in inert atmosphere upstream, composite wood
Material is placed in downstream, and high-temperature calcination in tube furnace obtains the cobalt sulfide nickel carbon nanotube-carbon nano-fiber composite wood of phosphorus doping
Material.
The preparation side of the cobalt sulfide nickel carbon nanotube-carbon nano-fiber composite material of phosphorus doping the most according to claim 1
Method, it is characterised in that the electrostatic spinning described in step (2), its technological parameter is: electrostatic field voltage 15 ~ 25 kV, spinning speed
Degree 0.2 ~ 0.4 mm min-1, receiving range 17 ~ 26 cm, the mass fraction of polyacrylonitrile is 7 % ~ 12 %, and CNT is with poly-
The mass ratio of acrylonitrile is 0.01 ~ 0.1.
The preparation side of the cobalt sulfide nickel carbon nanotube-carbon nano-fiber composite material of phosphorus doping the most according to claim 1
Method, it is characterised in that the pre-oxidation described in step (3), temperature is 220 ~ 280 DEG C, and preoxidation time is 1 ~ 2 h；Wherein control
Heating rate processed is 1 ~ 2 DEG C of min-1。
The preparation side of the cobalt sulfide nickel carbon nanotube-carbon nano-fiber composite material of phosphorus doping the most according to claim 1
Method, it is characterised in that the high temperature cabonization described in step (4), temperature is 800 ~ 1500 DEG C, and carbonization time is 1 ~ 3 h；Wherein institute
It is high-purity argon gas or high pure nitrogen with noble gas.
The preparation of the cobalt sulfide nickel carbon nanotube-carbon nano-fiber composite material of phosphorus doping the most according to claim 1
Method, it is characterised in that the cobalt salt described in step (5) is selected from cobalt chloride, cobalt nitrate, cobaltous acetate；Nickel salt selected from nickel nitrate,
Nickel dichloride., nickel sulfate；Sulfosalt is selected from thiourea, thioacetamide, sodium sulfide；Auxiliary agent is selected from carbamide, hexamethylenetetramine, second two
Amine；The consumption of cobalt salt is 10 ~ 30 mg mL-1;The consumption of nickel salt is 5 ~ 15 mg mL-1;The consumption of sulfosalt is 15 ~ 30 mg
mL-1, the consumption of auxiliary agent is 5 ~ 15 mg mL-1。
The preparation side of the cobalt sulfide nickel carbon nanotube-carbon nano-fiber composite material of phosphorus doping the most according to claim 1
Method, it is characterised in that in the hydro-thermal reaction described in step (6), the temperature of reaction is 150 ~ 200 DEG C, and the response time is 10 ~ 24
h。
The preparation side of the cobalt sulfide nickel carbon nanotube-carbon nano-fiber composite material of phosphorus doping the most according to claim 1
Method, it is characterised in that the phosphating reaction described in step (7), phosphorous presoma used is sodium hypophosphite, and consumption is compound fibre
5 ~ 20 times of dimension film, high-temperature calcination temperature is 300 ~ 900 DEG C.
8. the cobalt sulfide nickel carbon nanotube-carbon of the phosphorus doping prepared by the described preparation method of one of claim 1-7
Nano-fiber composite material.
9. the cobalt sulfide nickel carbon nanotube-carbon nano-fiber composite material of phosphorus doping as claimed in claim 8 is as high-performance
Electrocatalysis material and as lithium ion battery and the application of the electrode material of solaode.
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